EP1852199B1 - Poudre de fer enrobee d'oxyde contenant du magnesium - Google Patents

Poudre de fer enrobee d'oxyde contenant du magnesium Download PDF

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EP1852199B1
EP1852199B1 EP05805498A EP05805498A EP1852199B1 EP 1852199 B1 EP1852199 B1 EP 1852199B1 EP 05805498 A EP05805498 A EP 05805498A EP 05805498 A EP05805498 A EP 05805498A EP 1852199 B1 EP1852199 B1 EP 1852199B1
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Prior art keywords
iron powder
powder
ternary
film
oxide
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EP05805498A
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German (de)
English (en)
Japanese (ja)
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EP1852199A1 (fr
EP1852199A4 (fr
Inventor
Muneaki Watanabe
Ryoji Nakayama
Gakuji Uozumi
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Diamet Corp
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Diamet Corp
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Priority claimed from JP2005155206A external-priority patent/JP4761835B2/ja
Priority claimed from JP2005155207A external-priority patent/JP4761836B2/ja
Priority claimed from JP2005158892A external-priority patent/JP2006324612A/ja
Priority claimed from JP2005158893A external-priority patent/JP5027390B2/ja
Priority claimed from JP2005161479A external-priority patent/JP4480627B2/ja
Priority claimed from JP2005161480A external-priority patent/JP4480628B2/ja
Priority to EP12172935.4A priority Critical patent/EP2502689B8/fr
Application filed by Diamet Corp filed Critical Diamet Corp
Priority to EP10172637.0A priority patent/EP2248617B1/fr
Publication of EP1852199A1 publication Critical patent/EP1852199A1/fr
Publication of EP1852199A4 publication Critical patent/EP1852199A4/fr
Publication of EP1852199B1 publication Critical patent/EP1852199B1/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/33—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials mixtures of metallic and non-metallic particles; metallic particles having oxide skin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0207—Using a mixture of prealloyed powders or a master alloy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • H01F1/14766—Fe-Si based alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/20—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder
    • H01F1/22—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together
    • H01F1/24—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together the particles being insulated
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02K—DYNAMO-ELECTRIC MACHINES
    • H02K1/00—Details of the magnetic circuit
    • H02K1/02—Details of the magnetic circuit characterised by the magnetic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/32—Composite [nonstructural laminate] of inorganic material having metal-compound-containing layer and having defined magnetic layer

Definitions

  • the present invention relates to an iron powder coated with an oxide film containing MgO, having deposition films of Mg-Fe-O ternary-based oxide formed on surfaces of iron powder particles, where at least (Mg, Fe)O is contained in the deposition films and optionally ultra-fine particles of metallic iron are dispersed in the matrices of the deposition film, and to a deposition-film-coated iron powder for production of a composite soft magnetic material having high resistance.
  • the composite soft magnetic material made of the iron powder coated with the Mg-containing oxide film is used as a material for electromagnetic circuit components requiring low core loss (iron loss), for example, various electromagnetic components such as motors, actuators, yokes, cores and reactors.
  • the present invention also relates to composite soft magnetic powder formed by, on the surfaces of Mg-containing-iron-oxide-film-coated iron powder which are formed by coating Mg-Fe-O ternary-based oxide deposition films comprising at least (Mg,Fe)O on the surfaces of the iron powder particles, further coating MgO-SiO 2 composite oxide films (preferably forsterite having a MgO/SiO 2 value of 2 in molar ratio).
  • MgO-SiO 2 composite oxide films preferably forsterite having a MgO/SiO 2 value of 2 in molar ratio.
  • the present invention also relates to low core loss composite soft magnetic materials manufactured using the composite soft magnetic powder and having high strength, high magnetic flux density, and high resistance.
  • the low core loss composite soft magnetic materials having high strength, high magnetic flux density, and high resistance can be used as materials for various components of electromagnetic circuits requiring low core loss, for example, various electromagnetic components such as motors, actuators, yokes, rotors, cores and reactors.
  • a Mg-containing oxide film-coated iron powder formed by coating Mg-containing ferrite films having insulating property on the surfaces of the iron powder particles is known as an example of the above-described soft magnetic material having high resistivity (see Patent Reference 1).
  • a Mg-containing-chemical-conversion-film-coated powder formed by coating the Mg-containing-chemical-conversion-films on the surfaces of iron silicide powder particles is known as another example (see Patent Reference 2).
  • an iron-based Fe-Si-based soft magnetic powder containing 0.1 to 10 weight % of Si, and the balance consisting of Fe and unavoidable impurities is known as another example.
  • Soft magnetic powder formed by coating materials of high resistance on the surfaces of the iron-based Fe-Si-based soft magnetic powder particles is also known.
  • a manufacturing method of a composite soft magnetic material is known, where the soft magnetic material powder provided with the surface coating of high-resistance material is press-molded, and the obtained compact is heat-treated, thereby forming a composite soft magnetic material having high resistivity and a texture in which materials of high resistance exist in interstices of soft magnetic particles (see Patent Reference 3).
  • Patent References 4 or 5 Japanese Unexamined Patent Application, First Publication No. H11-1702 .
  • Patent Reference 2 Japanese Unexamined Patent Application, First Publication No. 2003-142310 .
  • Patent Reference 3 Japanese Unexamined Patent Application, First Publication No. H5-258934 .
  • Patent Reference 4 Japanese Unexamined Patent Application, First Publication No. 2004-253787 .
  • Patent Reference 5 Japanese Unexamined Patent Application, First Publication No. 2004-297036 .
  • JP 2003 217919 describes a dust core obtained by compressing and molding a magnetic powder of an alloy comprising 1 - 10 wt.% of Si, 0.1 - 1.0 wt.% of O and the remainder of Fe.
  • An insulator having SiO 2 and MgO as the main components is interposed between the pieces of the magnetic powder.
  • WO 01/58624 and EP 0 810 615 both describe soft magnetic particles having electric insulating layers on the surfaces thereof.
  • the insulating layers are formed by using an aqueous solution containing phosphoric acid, thus producing a phosphate coating.
  • the Mg-containing ferrite film is coated on the surface of the iron powder through a chemical process. Therefore, in the composite soft magnetic material obtained by performing high-temperature heat treatment for reducing strain of a press-molded compact, the ferrite film is destabilized and changed, and its insulation property is deteriorated. In addition, bonding of the Mg-containing ferrite film to the surface of the iron powder is not sufficient, and a composite soft magnetic material having sufficient strength cannot be manufactured by press molding and subsequently baking the Mg-containing iron oxide film-coated iron powder.
  • the Mg-containing ferrite film In composite soft magnetic materials manufactured by press molding and baking the Mg-containing oxide film-coated iron powder coated with the conventional Mg-containing ferrite film or by press molding and heat treating the mixed powder obtained by mixing the glass powder having a low melting point with the Mg-containing iron oxide film-coated iron powder coated with the Mg-containing ferrite film, the Mg-containing ferrite film cannot exert a sufficient insulation effect because of delamination during the press molding or the like, and therefore sufficient high temperature resistivity cannot be obtained.
  • the chemical conversion film formed by coating the above-described Mg-containing chemical conversion film by a chemical process is sometimes degraded during the high temperature baking treatment for removal of strain, thereby reducing the resisitance, and therefore, a complex soft magnetic material having sufficient high temperature resistivity cannot be obtained.
  • An Mg-containing ferrite oxide film may be considered as an example of high resistance material formed on the particle surface of the above-described iron-based Fe-Si-based soft magnetic powder.
  • an iron-based Fe-Si-based soft magnetic powder coated with the Mg-containing ferrite oxide film is press-molded into a compact, and strain-relief heat treatment at a high temperature is performed on the compact, sufficient high-temperature resistivity cannot be obtained.
  • the Mg-containing ferrite is generally unstable in relation to heat, its insulation property is easily reduced by the change of ferrite structure caused by heating. As a result, insulation property of the obtained composite soft magnetic material is reduced.
  • the Mg-containing ferrite oxide film is coated on the surface of powder particle through a chemical process. Therefore, bonding of the Mg-containing ferrite oxide film to the surface of iron-based Fe-Si-based soft magnetic powder particle is not sufficient. Therefore, in the composite soft magnetic material manufactured by press molding and heat-treating the iron-based soft magnetic powder coated with the conventional Mg-containing ferrite oxide film, delamination or breakdown of the Mg-containing ferrite oxide film or the like occur during press molding, and sufficient insulation effect cannot be exerted. Therefore, sufficient high resistivity could not be obtained.
  • the inventors performed research to manufacture a Mg-containing oxide film-coated iron powder having such properties that: the oxide film is firmly bonded to the surface of iron powder particle, and when the powder is press-molded, breakdown of a high resistance oxide film on the surface of the iron powder particle does not occur during the press molding; when strain-relief heat treatment at a high temperature is performed after press molding, surface insulation is not reduced, and the powder has high resistance, low eddy current loss; and a coercive force can be further reduced and hysteresis loss can be further reduced in the case of performing heat treatment of the powder for straightening annealing.
  • the below-described findings could be obtained.
  • iron powder hereafter referred to as oxidation-treated iron powder
  • oxidation-treated iron powder having a surface coating of iron oxide is formed by heating an iron powder in an oxidizing atmosphere.
  • the oxidation-treated iron powder is mixed with an Mg powder, and the obtained mixed powder is subjected to heating or the like in an inert gas atmosphere or in a vacuum atmosphere. After that, a second oxidization treatment is performed on the powder.
  • the present invention is made based on the above-described findings and has the following aspects.
  • the Mg-containing-oxide-film-coated iron powder of the present invention as described in (1) to (3) can be produced by: firstly producing an oxidation-treated iron powder by forming iron oxide films on the surfaces of iron powder particles by heating the iron powder in an oxidizing atmosphere, performing heating or the like in an inert gas atmosphere or in a vacuum atmosphere on the mixed powder obtained by mixing the oxidizing-treated iron powder with a Mg powder, and further performing a second oxidizing treatment to heat the mixed powder in an oxidizing atmosphere.
  • the Mg-containing-oxide-film-coated iron powder of the present invention may be produced by: firstly producing an oxidation-treated iron powder by forming iron oxide films on the surfaces of iron powder particles by heating the iron powder at a temperature of 50 to 500°C in an oxidizing atmosphere, heating the mixed powder obtained by mixing the oxidizing-treated iron powder with a Mg powder at a temperature of 150 to 1100°C in an inert atmosphere having a gas pressure of 1 ⁇ 10 -12 to 1 ⁇ 10 -1 MPa or in a vacuum atmosphere, and further performing a second oxidation treatment to heat the mixed powder at a temperature of 50 to 350°C in an oxidizing atmosphere.
  • the Mg-Fe-O ternary-based oxide deposition films containing a MgO-dissolving wustite phase and having an outermost surface substantially composed of MgO as described in the above-described (4) may be produced by: firstly producing oxidation-treated iron powder by forming iron oxide films on the surfaces of iron powder particles by heating the iron powder at a temperature of 50 to 500°C in an oxidizing atmosphere, heating the mixed powder obtained by mixing the oxidation-treated iron powder with a Mg powder of a further large amount at a temperature of 150 to 1100°C in an inert atmosphere having a gas pressure of 1 ⁇ 10 -12 to 1 ⁇ 10 -1 MPa or in a vacuum atmosphere, and further performing a second oxidizing treatment to heat the mixed powder for a further long duration in an oxidizing atmosphere.
  • the Mg-Fe-O ternary-based oxide deposition films formed on the surfaces of iron powder particles of the present invention contain at least (Mg,Fe)O.
  • the (Mg, Fe)O contained in the Mg-Fe-O ternary-based oxide film be a crystalline MgO-dissolving wustite.
  • the outermost surface of the deposition film at least containing (Mg, Fe)O may be composed of MgO.
  • the term "deposition film” indicates a film formed by depositing vacuum-evaporated or sputtered film-forming atoms, for example, on a substrate.
  • the Mg-Fe-O ternary-based oxide deposition film at least containing (Mg, Fe)O and formed on the surface of iron powder denotes a film deposited on the surface of the particles of iron powder being accompanied by reaction of Mg and iron oxide (Fe-O) on the particle surface of the oxidation-treated iron powder.
  • the Mg-Fe-O ternary-based oxide deposition film at least containing (Mg, Fe)O and formed on the surface of iron powder preferably has a film thickness in a range from 5 nm to 500 nm so as to ensure a high magnetic flux density and high resistivity of a composite soft magnetic material formed by compacting the powder.
  • the film thickness is smaller than 5 nm, it is not preferable, because the composite soft magnetic material formed by compacting the powder cannot have a sufficient resistivity and has an increased eddy current loss.
  • the film thickness is larger than 500 nm, it is not preferable because the composite soft magnetic material formed by compacting the powder has a decreased magnetic flux density. More preferably, the film thickness may be in a range from 5 nm to 200 nm.
  • the Mg-Fe-O ternary-based oxide film at least containing (Mg, Fe)O as a constituent of the Mg-containing-oxide-film-coated iron powder of the present invention has a sulfur-enriched layer at the boundary portion between the Mg-Fe-O ternary-based oxide film at least containing (Mg, Fe)O and the iron powder particle, where the sulfur concentration of the sulfur-enriched layer is higher than that of sulfur contained in the central portion of the iron powder particle.
  • the presence of the sulfur-enriched layer may be confirmed by an analysis of the sulfur concentration by Auger electron spectroscopy, where a peak of the sulfur concentration is shown in the graph.
  • the Mg-Fe-O ternary-based oxide film at least containing (Mg, Fe)O has further improved bonding to the surface of iron powder particle, breakdown of the deposition film is prevented by tracking of the deposition film to deformation of the powder at the time of press-molding the powder, high resistance is maintained by preventing contact and bonding of iron powder particles with each other at the time of heat treatment, and therefore eddy current loss is reduced.
  • the iron powder contains sulfur as unavoidable impurities. It is considered that most of the sulfur in the sulfur-enriched layer is provided by the sulfur contained in the surface portion of the iron powder.
  • the grain size of crystals constituting the Mg-Fe-O ternary-based oxide deposition film at least containing (Mg, Fe)O and formed on the surface of the iron powder particle of the present invention be as small as possible.
  • the deposition film has a fine crystalline texture having a grain size of 200 nm or less. Because the fine crystalline Mg-Fe-O ternary-based oxide deposition film has such a fine crystalline texture, the deposition film tracks the deformation of powder particle during formation of the compact, and is prevented from breakdown. At the time of heat treatment, the iron powder particles are prevented from contacting and bonding with each other.
  • the powder When the powder is subjected to strain-relief heat treatment at a high temperature, because of the stable property of the oxide, reduction of insulation is prevented, and eddy current loss is lowered.
  • the grain size is larger than 200 nm, it is not preferable, because the film thickness of the Mg-Fe-O ternary-based oxide deposition film exceeds 500 nm, and magnetic flux density of compacted composite soft magnetic material is reduced.
  • the MgO content in the outermost surface of the Mg-Fe-O ternary-based oxide deposition film at least containing (Mg, Fe)O and constituting the Mg-containing oxide film-coated iron powder of the present invention is preferably as high as possible. It is most preferable that the outermost surface be substantially composed of MgO. Where the outermost surface is substantially MgO, diffusion of Fe is inhibited at the time of heat treatment of the press-molded compact, the iron powder particles are prevented from contacting and bonding with each other, reduction of insulation is prevented, high resistance is ensured, and eddy current loss is lowered.
  • the above-described Mg-Fe-O ternary-based oxide deposition film at least containing (Mg,Fe)O and constituting the Mg-containing oxide-film coated iron powder of the present invention may be a pseudo ternary oxide film in which 10% or less of Mg is replaced by one or more elements selected from Al, Si, Ni, Mn, Cu, and Co.
  • the powder having a mean grain size in a range from 5 to 500 ⁇ m.
  • the reason for this limitation is explained as follows. Where the mean grain size is smaller than 5 ⁇ m, it is not preferable, because the compressibility of the powder is lowered and volume fraction of the powder is decreased, and therefore the value of magnetic flux density is lowered. On the other hand, where the mean grain size is larger than 500 ⁇ m, eddy current in the powder is increased, and magnetic permeability at high frequency is reduced.
  • a Mg-containing oxide film-coated iron powder of the present invention may be subjected to compacting and heat treatment in accordance with a usual method.
  • the composite soft magnetic material produced using the Mg-containing oxide film-coated iron powder of the present invention is constituted of an iron particle phase and grain boundary phase surrounding the iron particle phase, where the grain boundary phase contains Mg-Fe-O ternary-based oxide including crystalline MgO-dissolving wustite phase.
  • the soft magnetic material may be produced by preparing a mixed powder such that 0.05 to 1% weight of one or two selected from silicon oxide and aluminum oxide each having a grain size of 0.5 ⁇ m or less and the balance consisting of the Mg-containing oxide film-coated iron powder of the present invention are blended in the mixed power, compacting, and heat-treating the mixed powder in accordance with the usual method.
  • the Mg-Fe-O ternary-based oxide deposition film at least containing (Mg, Fe)O and constituting the Mg-containing oxide film-coated iron powder of the present invention reacts with the silicon oxide and/or aluminum oxide to form a complex oxide.
  • the iron powder is heat-treated interposing the silicon oxide and/or aluminum oxide, it is possible to produce a composite soft magnetic material having excellent mechanical strength.
  • the silicon oxide and/or the aluminum oxide have a main role in the heat treatment, a coercive force can be maintained at a low value, and therefore, it is possible to produce a composite soft magnetic material having low hysteresis loss. It is preferable that the above-described heat treatment be performed at a temperature of 400 to 1300°C in an inert gas atmosphere or in an oxidizing gas atmosphere.
  • a composite soft magnetic material may be produced by mixing the Mg-containing oxide film-coated iron powder of the present invention and a wet solution such as a sol-gel (silicate) solution of silica and sol-gel solution of alumina added to the powder, drying the mixture of the powder and the solution, compacting the dried mixture, and heat-treating the compacted mixture at a temperature of 400 to 1300°C in an inert gas atmosphere or in an oxidizing gas atmosphere.
  • a wet solution such as a sol-gel (silicate) solution of silica and sol-gel solution of alumina added to the powder, drying the mixture of the powder and the solution, compacting the dried mixture, and heat-treating the compacted mixture at a temperature of 400 to 1300°C in an inert gas atmosphere or in an oxidizing gas atmosphere.
  • These composite soft magnetic materials produced using the Mg-containing oxide film-coated iron powder of the present invention are constituted of an iron particle phase and grain boundary phase surrounding the iron particle phase, where the grain boundary phase includes Mg-Fe-O ternary-based oxides including a crystalline MgO-dissolving wustite phase.
  • a composite soft magnetic material having further improved resistivity and strength may be produced by mixing the Mg-containing oxide film-coated iron powder of the present invention with an organic insulating material, inorganic insulating material, or a mixture of an organic insulating material and inorganic insulating material, compacting the mixed material, and heat-treating the compacted material.
  • an organic insulating material inorganic insulating material, or a mixture of an organic insulating material and inorganic insulating material, compacting the mixed material, and heat-treating the compacted material.
  • epoxy resin, fluororesin, phenol resin, urethane resin, silicone resin, polyester resin, phenoxy resin, urea resin, isocyanate resin, acrylic resin, polyimide resin or the like may be applied as the organic insulating material.
  • Phosphate such as iron phosphate, various glassy insulating materials, water glass mainly composed of sodium silicate, insulating oxide or the like may be applied as the inorganic insulating material
  • a composite soft magnetic material may be produced by mixing the Mg-containing oxide film-coated iron powder of the present invention with one or two or more selected from boron oxide, vanadium oxide, bismuth oxide, antimony oxide, and molybdenum oxide such that, in reduced mass of B 2 O 3 , V 2 O 5 , Bi 2 O, Sb 2 O 3 ,and MoO 3 , 0.05 to 1 weight % is blended in the mixture, compacting the mixture, and heat-treating the compact at a temperature of 500 to 1000°C.
  • the thus produced composite soft magnetic material has a composition containing, in reduced mass of B 2 O 3 , V 2 O 5 , Bi 2 O 3 , Sb 2 O 3 , and MoO3, 0.05 to 1 weight % of one or more selected from boron oxide, vanadium oxide, bismuth oxide, antimony oxide, and molybdenum oxide, and the balance consisting of Mg-containing oxide film-coated iron powder of the present invention.
  • films are formed by the reaction of the Mg-Fe-O ternary-based oxide deposition films at least containing (Mg,Fe)O and one or more selected from boron oxide, vanadium oxide, bismuth oxide, antimony oxide, and molybdenum oxide.
  • the composite soft magnetic material may be produced by blending one or more selected from a sol solution or powder of boron oxide, sol solution or powder of vanadium oxide, sol solution or powder of bismuth oxide, sol solution or powder of antimony oxide, and sol solution or powder of molybdenum oxide such that the mixture has a composition containing, in reduced mass of B 2 O 3 , V 2 O 5 , Bi 2 O 3 , Sb 2 O 3 , and MoO 3 , 0.05 to 1 weight %, and the balance consisting of Mg-containing oxide film-coated iron - powder of the present invention, mixing and drying the mixture, thereby producing mixed-oxide film-coated iron powder made by coating the dried gel or powder of the mixed oxide on the Mg-containing oxide film-coated iron powder of the present invention, compacting and molding the mixed-oxide-coated iron powder, and heat-treating the compact at a temperature of 500 to 1000°C.
  • These composite soft magnetic materials having high resistivity and produced using the Mg-containing oxide film-coated iron powder of the present invention is constituted of an iron particle phase and grain boundary phase surrounding the iron particle phase where the grain boundary phase includes Mg-Fe-O ternary-based oxide including crystalline MgO-dissolving wustite phase.
  • the composite soft magnetic material produced using the Mg-containing oxide film-coated iron powder of the present invention has high density, high strength, and high magnetic flux density.
  • the composite soft magnetic material having high magnetic flux density and high frequency core loss may be applied as a material of various electromagnetic circuit components utilizing the above-described properties. Examples of the above-described electromagnetic circuit components include a magnetic core, core of a motor, core of a generator, solenoid core, ignition core, reactor, transformer, core of a choke coil, and core of a magnetic sensor or the like.
  • the electromagnetic circuit component comprising the composite soft magnetic material having high resistance and utilizing the Mg-containing oxide film-coated iron powder of the present invention may be equipped to electric apparatuses such as a motor, generator, solenoid, injector, electromagnetic valve, inverter, converter, transformer, potential transformer, electric relay, magnetic sensor or the like, and contributes to improving efficiency and performance, downsizing, and weight saving of the apparatuses.
  • electric apparatuses such as a motor, generator, solenoid, injector, electromagnetic valve, inverter, converter, transformer, potential transformer, electric relay, magnetic sensor or the like, and contributes to improving efficiency and performance, downsizing, and weight saving of the apparatuses.
  • the inventors performed research to manufacture a Mg-containing oxide film-coated iron powder having such properties that: the oxide film is firmly bonded to the surface of iron powder particle, and when the powder is press-molded, breakdown of a high resistance oxide film on the surface of iron powder does not occur during the press molding; when strain-relief heat treatment at a high temperature is performed after press molding, surface insulation is not reduced, and the powder has high resistance, low eddy current loss; and a coercive force can be further reduced and hysteresis loss can be reduced in the case of performing heat treatment of the powder for straightening annealing.
  • an iron powder (hereafter referred to as oxidation-treated iron powder) having a surface coating of iron oxide is formed by heating an iron powder in an oxidizing atmosphere.
  • the oxidation-treated iron powder is mixed with an Mg powder, and the obtained mixed powder is subjected to heating in an inert gas atmosphere or in an vacuum atmosphere while tumbling (rolling) the powder.
  • the present invention is made based on the above-described findings and has the following aspects.
  • the Mg-containing oxide film-coated iron powder of the present invention as described in the above-described (8) to (11) is produced by forming a oxidation-treated iron powder by heating iron powder in an oxidizing atmosphere, adding Mg powder to the oxidation-treated iron powder and mixing the powder, and heating thus obtained mixed powder in an inert gas atmosphere or in a vacuum atmosphere while tumbling the mixed powder.
  • oxidation-treated iron powder having iron oxide films formed on the surfacesof iron powder particles is produced by preliminary heating the iron powder in an oxidizing atmosphere at a temperature of 50 to 500°C.
  • Mg powder is added to and mixed with the oxidation-treated iron powder. While being rolled, obtained mixed powder is heated at a temperature of 150 to 1100°C in an inert gas atmosphere or in a vacuum atmosphere having a pressure of 1 ⁇ 10 -12 to 1 ⁇ 10 -1 MPa.
  • the Mg-Fe-O ternary-based oxide deposition film comprising ultra-fine grained metallic Fe dispersed in the matrix and having an outermost surface substantially composed of MgO as described in the above-described (12) may be produced by:
  • deposition film is a term denoting a film made of vacuum evaporated or sputtered film-forming atoms deposited on the surface of, for example, a substrate.
  • the Mg-Fe-O ternary-based oxide deposition film formed on the surface of the iron powder of the present invention and comprising ultra-fine grained metallic Fe particles in the matrix denotes a film deposited on the surface of particles of the iron powder being accompanied with a reaction of Mg and iron oxide (Fe-O) on the particle surface of the oxidation-treated iron powder.
  • the Mg-Fe-O ternary-based oxide deposition film according to the present invention comprising ultra-fine grained metallic Fe particles dispersed in the matrix has a high toughness. Therefore, the deposition film sufficiently tracks the deformation of the iron powder particle at the time of press molding, and has remarkably excellent adherence to the iron powder particle.
  • the Mg-Fe-O ternary-based oxide deposition film according to the present invention comprising ultra-fme grained metallic Fe grains dispersed in the matrix contains crystalline MgO-dissolving wustite. More preferably, the MgO-dissolving wustite has a crystalline structure.
  • the Mg-Fe-O ternary-based oxide deposition film formed on the surface of the iron powder particle of the present invention and comprising ultra-fine grained metallic Fe grains dispersed in the matrix has a film-thickness in a range from 5 to 500 nm so as to ensure high magnetic flux density and high resistivity of the composite soft magnetic material formed by compacting the powder.
  • the film thickness is smaller than 5nm, it is not preferable, since the resistivity is not sufficient and eddy current loss is increased in the composite soft magnetic material formed by compacting the powder.
  • the film thickness is larger than 500 nm, it is not preferable since the magnetic flux density is decreased in the composite soft magnetic material formed by compacting the powder. More preferably, the film thickness is in a range from 5 to 200 nm.
  • the Mg-Fe-O ternary-based oxide deposition film constituting the Mg-containing oxide-coated iron powder of the present invention and comprising ultra-fine grained metallic Fe particles dispersed in the matrix preferably has a concentration gradient such that Mg and O decrease from exterior surface to the interior direction, and Fe increase to the interior. Because of such a concentration gradient, the oxide film has further excellent adherence to the iron powder. Therefore, there is a lesser possibility of breakdown of the oxide film as the insulation film during the press molding of the powder. The oxide film escapes from deterioration of insulation property and maintains high resistance even when the press-molded powder is subjected to strain-relief heat treatment at a high temperature. Therefore, eddy current loss is lowered.
  • a sulfur-enriched layer containing a higher concentration of sulfur than the sulfur concentration of the central portion of the iron particle of the iron powder exists in the boundary portion between the iron particle and the Mg-Fe-O ternary-based oxide deposition film comprising ultra-fine grained metallic Fe dispersed in the matrix.
  • the oxide film has further excellent bonding to the iron powder. Therefore, the deposition film tracks the deformation of the particle during compacting the powder, and breakdown of the coating is inhibited.
  • iron powder particles are prevented from being made to contact and bonded with each other, and resistivity of the oxide film is maintained. Therefore, eddy current loss is lowered. It is considered that the sulfur in the sulfur-enriched layer is provided from unavoidable impurities contained in the iron powder.
  • the Mg-Fe-O ternary-based oxide deposition film constituting the Mg-containing oxide-coated iron powder of the present invention and comprising ultra-fine grained metallic Fe grains dispersed in the matrix preferably has as small a grain size as possible, and preferably has ultra-microcrystalline structure having a grain size of 200 nm or less.
  • the ultra-fine grained crystalline deposition film tracks the deformation of powder particle at the time of compacting the powder, and breakdown of the coating is inhibited. In addition, the powder is prevented from being made to contact with each other even at the time of heat treatment.
  • the oxide is stable, be prevented from reduction of insulation property, and maintains high resistance. Therefore, eddy current loss is lowered.
  • the grain size is larger than 200 nm, film thickness of the deposition film exceeds 500 nm, and magnetic flux density of the composite soft magnetic material is reduced.
  • the Mg-Fe-O ternary-based oxide deposition film comprising ultra-fine metallic Fe grains dispersed in the matrix preferably contains as high a MgO content as possible in the outermost surface.
  • the outermost surface of the film is substantially composed of MgO.
  • the outermost surface of the film is substantially MgO, at the time of heat treatment of the press-molded compact, diffusion of Fe is inhibited, the iron powder particles are prevented from contacting and bonding with each other, and reduction of insulation property is prevented, high resistance is maintained, and eddy current loss is lowered.
  • the Mg-Fe-O ternary-based oxide deposition film constituting the Mg-containing oxide-coated iron powder of the present invention and comprising ultra-fine grained metallic Fe particles dispersed in the matrix may be a pseudo ternary oxide deposition film in which Mg is partially replaced by one or more selected from Al, Si, Mn, Zn, Cu, and Co such that 10 atomic % or less of Mg is replaced.
  • the Mg-containing oxide film-coated iron powder of the present invention it is preferable to use a powder having a mean grain size in a range from 5 to 500 ⁇ m.
  • the reason is explained as follows. Where the mean grain size is smaller than 5 ⁇ m, it is not preferable, since compressibility of the powder is lowered, volume fraction of the powder is lowered, and therefore magnetic flux density is lowered. On the other hand, where the mean grain size is too larger than 500 ⁇ m, eddy current in the intrerior of the powder particle is increased and magnetic permeability at high frequency is reduced.
  • the composite soft magnetic material according to the present invention having higher resistivity than that of the conventional one can be produced by press molding and heat-treating the Mg-containing oxide film-coated iron powder of the present invention in accordance with the usual process.
  • a texture of the thus produced composite soft magnetic material of the present invention is constituted of an iron particle phase generated from the iron powder and grain boundary phase surrounding the iron particle phase.
  • the above-described grain boundary phase contains Mg-Fe-O ternary-based oxide including crystalline MgO-dissolving wustite.
  • the composite soft magnetic material may be produced by producing a mixed powder such that 0.05 to 1 mass % of one or two selected from silicon oxide and aluminum oxide having a mean grain size of 0.5 ⁇ +m or less and the balance consisting of the Mg-containing-oxide-film-coated iron powder according to the present invention are blended and mixed in the mixed powder; compacting and heat-treating the mixed powder in accordance with the usual method.
  • the Mg-Fe-O ternary-based oxide deposition film constituting the Mg-containing oxide film-coated iron powder of the present invention and comprising ultra-fine grained metallic Fe grains dispersed in the matrix reacts with silicon oxide and/or aluminum oxide and forms complex oxide.
  • the composite soft magnetic material having high resistivity in which complex oxide having high resistance exists in grain boundary of the iron powder, is obtained.
  • the composite soft magnetic material having high mechanical strength can be produced.
  • the silicon oxide and/or aluminum oxide have a main roll in the heat treatment, small value of coercive force can be maintained. Therefore it is possible to produce a composite soft magnetic material having low hysteresis loss.
  • the above-described heat treatment is performed in an inert gas atmosphere or in an oxidizing gas atmosphere at a temperature of 400 to 1300°C.
  • a composite soft magnetic material may be produced by mixing the Mg-containing oxide film-coated iron powder of the present invention and a wet solution such as a sol-gel (silicate) solution of silica and sol-gel solution of alumina added to the powder, drying the mixture of the powder and the solution, compacting the dried mixture, and heat-treating the compacted mixture at a temperature of 400 to 1300°C in an inert gas atmosphere or in an oxidizing gas atmosphere.
  • a composite soft magnetic material having further improved resistivity and strength may be produced by mixing the Mg-containing oxide film-coated iron powder of the present invention with an organic insulating material, inorganic insulating material, or a mixture of organic insulating material and inorganic insulating material.
  • organic insulating material inorganic insulating material, or a mixture of organic insulating material and inorganic insulating material.
  • epoxy resin, fluororesin, phenol resin, urethane resin, silicone resin, polyester resin, phenoxy resin, urea resin, isocyanate resin, acrylic resin, polyimide resin or the like may be applied as the organic insulating material.
  • Phosphate such as iron phosphate, various glassy insulating materials, water glass mainly composed of sodium silicate, insulating oxide or the like may be applied as the inorganic insulating material.
  • a composite soft magnetic material may be produced by mixing the Mg-containing oxide film-coated iron powder of the present invention with one or two or more selected from boron oxide, vanadium oxide, bismuth oxide, antimony oxide, and molybdenum oxide such that, in reduced mass of B 2 O 3 , V 2 0 5 , Bi 2 O 3 , Sb 2 O 3 ,and MoO 3 0.05 to 1 mass % is blended on the mixture, compacting the mixture, and heat-treating the compact at a temperature of 500 to 1000°C.
  • the thus produced composite soft magnetic material has a composition containing, in reduced mass of B 2 O 3 , V 2 O 5 , Bi 2 O 3 , Sb 2 O 3 , and MoO 3 , 0.05 to I mass % of one or more selected from boron oxide, vanadium oxide, bismuth oxide, antimony oxide, and molybdenum oxide, and the balance consisting of Mg-containing oxide film-coated iron powder of the present invention.
  • films are formed by the reaction of the Mg-Fe-O ternary-based oxide deposition films comprising extremely fine grained metallic Fe particles dispersed in the matrix and one or more selected from boron oxide, vanadium oxide, bismuth oxide, antimony oxide, and molybdenum oxide.
  • the composite soft magnetic material may be produced by blending one or more selected from a sol solution or powder of boron oxide, sol solution or powder of vanadium oxide, sol solution or powder of bismuth oxide, sol solution or powder of antimony oxide, and sol solution or powder of molybdenum oxide such that the mixture has a composition containing, in reduced mass of B 2 O 3 , V 2 O 5 , Bi 2 O 3 , Sb 2 O 3 , and MoO 3 , 0.05 to 1 mass %, and the balance consisting of Mg-containing oxide film-coated iron powder of the present invention, mixing and drying the mixture, thereby producing mixed-oxide film-coated iron powder made by coating the dried gel or powder of the mixed oxide on the Mg-containing oxide film-coated iron powder of the present invention, compacting and molding the mixed-oxide-coated iron powder, and heat-treating the compact at a temperature of 500 to 1000°C.
  • the composite soft magnetic materials produced in accordance with the above-described method using Mg-containing oxide film-coated iron powder of the present invention are each constituted of an iron particle phase generated from the iron powder in the Mg-containing oxide film-coated iron powder, and grain boundary phase surrounding the iron particle phase.
  • the grain boundary phase contains Mg-Fe-O ternary-based oxides including crystalline MgO-dissolving wustite.
  • the composite soft magnetic material produced using the Mg-containing oxide film-coated iron powder of the present inventin has high density, high strength, and high magnetic flux density.
  • the composite soft magnetic material having high magnetic flux density and low core loss at high frequency may be applied as a material of various electromagnetic circuit components utilizing the above-described properties. Examples of the above-described electromagnetic circuit components include a magnetic core, core of a motor, core of a generator, solenoid core, ignition core, reactor, transformer, core of a choke coil, and core of a magnetic sensor or the like.
  • the electromagnetic circuit component comprising the composite soft magnetic material having high resistance and utilizing the Mg-containing oxide film-coated iron powder of the present invention may be equipped to electric apparatuses such as a motor, generator, solenoid, injector, electromagnetic valve, inverter, converter, transformer, potential transformer, electric relay, magnetic sensor or the like, and contributes to improving efficiency and performance, downsizing, and weight saving of the apparatuses.
  • electric apparatuses such as a motor, generator, solenoid, injector, electromagnetic valve, inverter, converter, transformer, potential transformer, electric relay, magnetic sensor or the like, and contributes to improving efficiency and performance, downsizing, and weight saving of the apparatuses.
  • the inventors performed research to manufacture a high resistance film-coated iron powder having such properties that: the high resistance film is firmly bonded to the surface of iron powder, and when the powder is press-molded, breakdown of a high resistance oxide film on the surface of iron powder particle does not occur during the press molding; when strain-relief heat treatment at high temperature is performed after press molding, surface insulation is not reduced, and the powder has high resistance, low eddy current loss; and a coercive force can be further reduced and hysteresis loss can be reduced in the case of performing heat treatment of the powder for straightening annealing.
  • the below-described findings could be obtained. 1000°C.
  • the composite soft magnetic material produced using the oxide deposition film-coated iron-based Fe-Si-based soft magnetic powder of the present invention has high density, high strength, high resistivity, and high magnetic flux density.
  • the composite soft magnetic material having high magnetic flux density and high frequency core loss may be applied as a material of various electromagnetic circuit components utilizing the above-described properties. Examples of the above-described electromagnetic circuit components include a magnetic core, core of a motor, core of a generator, solenoid core, ignition core, reactor, transformer, core of a choke coil, and core of a magnetic sensor or the like.
  • the electromagnetic circuit component comprising the composite soft magnetic material having high resistance and utilizing the oxide deposition film-coated iron-based Fe-Si-based soft magnetic powder of the present invention may be equipped to electric apparatuses such as a motor, generator, solenoid, injector, elenctromagnetic valve, inverter, converter, potential transformer, electric relay, magnetic sensor system or the like, and contributes to improving efficiency and performance, downsizing, and weight saving of the apparatuses.
  • electric apparatuses such as a motor, generator, solenoid, injector, elenctromagnetic valve, inverter, converter, potential transformer, electric relay, magnetic sensor system or the like, and contributes to improving efficiency and performance, downsizing, and weight saving of the apparatuses.
  • Mg-containing iron oxide film-coated iron powder such as described in the following (a) to (e).
  • the previously invented Mg-containing iron oxide film-coated iron powders as described in the above (a), (d) or (e) were obtained by: firstly forming an iron powder (hereafter referred to as oxidation-treated iron powder) having a surface coating of iron oxide by subjecting the iron powder to an oxidization treatment, for example, heating the iron powder in an oxidizing atmosphere; adding an Mg powder to the oxidation-treated iron powder and mixing the powder; subjecting the obtained mixed powder to heating or the like in an inert gas atmosphere or in an vacuum atmosphere; and further performing a second oxidization treatment to heat the powder in an oxidizing atmosphere.
  • the invention of these previously invented Mg-containing iron oxide film-coated iron powder were made based on the findings such as described in the following.
  • the Mg-containing iron oxide film-coated iron powder of the previous invention as described in (a) to (d) can be produced by: firstly producing an oxidizing-treated iron powder by forming an iron oxide film on the surface of iron powder by heating the iron powder at a temperature of 50 to 500°C in an oxidizing atmosphere; adding Mg powder to the oxidizing-treated iron powder and mixing the powder; heating the obtained mixed powder at a temperature of 150 to 1100°C in an inert atmosphere having a gas pressure of 1 ⁇ 10 -12 to 1 ⁇ 10 -1 MPa or in a vacuum atmosphere; and where necessary, further performing a second oxidizing treatment after heating the mixed powder at a temperature of 50 to 350°C in an oxidizing atmosphere.
  • the Mg-Fe-O ternary-based oxide deposition film containing MgO-dissolving wustite phase and having an outermost surface substantially composed of MgO as described in the above (e) may be produced by: firstly producing an oxidizing-treated iron powder by forming an iron oxide film on the surface of iron powder by heating the iron powder at a temperature of 50 to 500°C in an oxidizing atmosphere; adding a Mg powder of a further large amount to the oxidizing-treated iron powder and mixing the powder; heating the mixed powder at a temperature of 150 to 1100°C in an inert atmosphere having a gas pressure of 1 ⁇ 10 -12 to 1 ⁇ 10 -1 MPa or in a vacuum atmosphere; and further performing a second oxidizing treatment to heat the mixed powder for a further long duration in an oxidizing atmosphere.
  • the term "deposition film” indicates a film formed by depositing vacuum-evaporated or sputtered film-forming atoms, for example, on a substrate.
  • the Mg-Fe-O ternary-based oxide deposition film at least containing (Mg,Fe)O and formed on the surface of iron powder denotes a film deposited on the surface of iron powder particle being accompanied by reaction of Mg and iron oxide (Fe-O) on the surface of the iron powder particle having an iron oxide film.
  • the Mg-Fe-O ternary-based oxide deposition film at least containing (Mg,Fe)O and formed on the surface of iron powder preferably has a film thickness in a range from 5 nm to 500 nm so as to ensure a high magnetic flux density and high resistivity of a composite soft magnetic material formed by compacting the powder.
  • the film thickness is smaller than 5 nm, it is not preferable, because the composite soft magnetic material formed by compacting the powder cannot have a sufficient resistivity, and eddy current loss is increased.
  • the film thickness is larger than 500 nm, it is not preferable because magnetic flux density is decreased in the composite soft magnetic material formed by compacting the powder. More preferably, the film thickness may be in a range of 5 nm to 200 nm.
  • the Mg-Fe-O ternary-based oxide film at least containing (Mg, Fe)O formed on the surface of the previously invented Mg-containing iron oxide film-coated iron powder as described in the above (a) to (e) has a sulfur-enriched layer at the boundary portion between the Mg-Fe-O ternary-based oxide film at least containing (Mg, Fe)O and the iron powder particle, where the sulfur concentration of the sulfur-enriched layer is higher than that of sulfur contained in a central portion of the iron powder particle.
  • the presence of the sulfur-enriched layer may be confirmed by performing analysis of the sulfur concentration by Auger electron spectroscopy, showing the results of the analysis, where a peak of the sulfur concentration is shown in the graph.
  • the Mg-Fe-O ternary-based oxide film at least containing (Mg, Fe)O has further improved bonding to the surface of iron powder, breakdown of the deposition film is prevented by tracking of the deposition film to deformation of the powder at the time of press molding the powder. High resistance is maintained by preventing contact and bonding of iron powder particles with each other at the time of heat treatment, and therefore eddy current loss is reduced.
  • the iron powder contains sulfur as unavoidable impurities. It is considered that most of the sulfur in the sulfur-enriched layer is provided by the sulfur contained in the surface portion of the iron powder.
  • the grain size of crystals constituting the Mg-Fe-O ternary-based oxide deposition film at least containing (Mg, Fe)O and formed on the surface of the Mg-containing iron oxide film-coated iron powder of the above (a) to (e) is as small as possible.
  • the deposition film has a fine crystalline texture having a grain size of 200 nm or less. Because the film has such a fine crystalline texture, the fine crystalline Mg-Fe-O ternary-based oxide deposition film tracks the deformation of powder particle at the time of compacting the powder, and is prevented from breakdown. At the time of heat treatment, the iron powder is prevented from being made to contact and bonded with each other.
  • the powder When the powder is subjected to strain-relief heat treatment at a high temperature, because of the stable property of the oxide, reduction of insulation is prevented, high resistance is maintained, and eddy current loss is lowered.
  • the grain size is larger than 200 nm, it is not preferable, because the film thickness of the Mg-Fe-O ternary-based oxide deposition film exceeds 500 nm, and magnetic flux density of compacted composite soft magnetic material is reduced.
  • the MgO content in the outermost surface of the Mg-Fe-O ternary-based oxide deposition film at least containing (Mg, Fe)O and formed on the surface of the Mg-containing iron oxide film-coated iron powder of the above (e) is preferably as high as possible. It is most preferable that the outermost surface is substantially composed of MgO. Where the outermost surface is substantially MgO, diffusion of Fe is inhibited at the time of heat treatment of the press-molded compact, the iron powder particles are prevented from contacting and bonding with each other, reduction of insulation is prevented, high resistance is ensured, and eddy current loss is lowered.
  • An object of the present invention is to provide a composite soft magnetic powder having further improved compressibility and sinterability, and a method of producing the powder.
  • Such a powder may be provided by further coating MgO-SiO 2 composite oxide film having a MgO/SiO 2 value in a range from 1.0 to 3.0 in molar ratio on the surface of the previously invented Mg-containing iron oxide film-coated iron powder as described in (a) to (e).
  • MgO-SiO 2 composite oxide film has a high electric insulation property and relatively soft hardness (1 to 4 in Mohs hardness), is enriched in antifrictional action and lubricating action, and acts as lubricant at the time of compacting the powder. Therefore, the composite soft magnetic powder having MgO-SiO 2 oxide deposition film formed on the surface of the previously invented Mg-containing iron oxide film-coated iron powder as described in the above (a) to (e) has further improved compressibility.
  • composite soft magnetic powder of the present invention having MgO-SiO 2 oxide deposition film coated on the particle surface of the Mg-containing iron oxide film-coated iron powder as described in the above (a) to (e) has further improved sinterability.
  • a composite soft magnetic powder as defined above comprising:Mg-containing iron oxide film-coated iron powder particles having iron powder particles and Mg-Fe-O ternary-based oxide deposition films which contain at least (Mg, Fe)O and are formed on surfaces of the iron powder particles; and MgO-SiO 2 composite oxide film which have a MgO/SiO 2 value in a range from 1.0 to 3.0 in molar ratio and are further coated on surfaces of the Mg-containing iron oxide film-coated iron powder particles.
  • a composite soft magnetic powder as defined above comprising:Mg-containing iron oxide film-coated iron powder particles having iron powder particles, Mg-Fe-O ternary-based oxide deposition films which contain at least (Mg, Fe)O and are coated on surfaces of the iron powder particles, and sulfur-enriched layers in boundary portions between the iron powder particles and the Mg-Fe-O ternary-based oxide deposition films at least containing (Mg, Fe)O; and MgO-SiO 2 composite oxide films which have a MgO/SiO 2 value in a range from 1.0 to 3.0 in molar ratio and are further coated on surfaces of the Mg-containing iron oxide film-coated iron powder particles, wherein sulfur concentrations of the sulfur-enriched layers are higher than that of sulfur contained as an unavoidable impurity in central portions of the iron powder particles.
  • the composite soft magnetic powder of the present invention as described in the above (48), (49), (51) and (52) may be produced by: preparing a mixed oxide sol-solution of MgO and SiO 2 obtained by mixing, in volumetric ratio, alkoxysilane solution:1 and magnesium-alkoxide solution:1 to 3; adhering the sol-solution to the surface of the Mg-containing iron oxide film-coated iron powder as described in the above (a) to (e); and heating and drying the powder.
  • Mg-containing oxide film-coated iron powder such as described in the following (f) to (k).
  • the previously invented Mg-containing oxide film-coated iron powder as described in the above (f), (g), (h), (j), or (k) is obtained by: firstly forming an iron powder (hereafter referred to as oxidation-treated iron powder) having a surface coating of iron oxide by performing oxidization treatment, for example, by heating the iron powder in an oxidizing atmosphere; adding Mg powder to the oxidation-treated iron powder and mixing the powder; heating thus obtained mixed powder in an inert gas atmosphere or in a vacuum atmosphere while tumbling the mixed powder; and further performing second oxidization treatment of the powder by heating the powder in an oxidizing atmosphere.
  • oxidation-treated iron powder having a surface coating of iron oxide
  • the obtained Mg-Fe-O ternary-based oxide deposition film of the previously invented Mg-containing iron oxide-coated iron powder was formed based on the findings as described in the following.
  • oxidation-treated iron powder having an iron oxide film formed on the surface of iron powder is produced by preliminary heating the iron powder in an oxidizing atmosphere at a temperature of 50 to 500°C.
  • Mg powder is added to and mixed with the oxidation-treated iron powder. While being rolled, obtained mixed powder is heated at a temperature of 150 to 1100°C in an inert gas atmosphere or in a vacuum atmosphere having a pressure of 1 ⁇ 10 -12 to 1 ⁇ 10 -1 MPa.
  • a second oxidization treatment is further performed, where the powder is heated at a temperature of 50 to 350°C in an oxidizing atmosphere.
  • Mg-Fe-O ternary-based oxide deposition film comprising ultra-fine grained metallic Fe dispersed in the matrix and having an outermost surface substantially composed of MgO as described in the above-described (k) may be produced by: forming an oxidation-treated iron powder having an iron oxide film formed on the surface of iron powder by preliminary heating the iron powder in an oxidizing atmosphere at a temperature of 50 to 500°C; adding further large amount of Mg powder to the oxidation-treated iron powder having the relatively thick iron oxide film and mixing the powder; heating thus obtained mixed powder at a temperature of 150 to 1100°C in an inert gas atmosphere or in a vacuum atmosphere having a pressure of 1 ⁇ 10 -12 to 1 ⁇ 10 -1 MPa, while tumbling the mixed powder; and further performing second oxidization treatment where the powder is heated at a temperature of 50 to 350°C in an oxidizing atmosphere for a further long duration.
  • deposition film is a term denoting a film made of vacuum evaporated or sputtered film-forming atoms deposited on the surface of, for example, a substrate.
  • the Mg-Fe-O ternary-based oxide deposition film formed on the surface of the iron powder of the present invention and comprising ultra-fine grained metallic Fe particles in the matrix denotes a film deposited on the surface of the iron powder particle being accompanied with a reaction of Mg and iron oxide (Fe-O) on the surface of the oxidation-treated iron powder.
  • the Mg-Fe-O ternary-based oxide deposition film according to the present invention comprising ultra-fine grained metallic Fe particles dispersed in the matrix has a high toughness. Therefore, the deposition film sufficiently tracks the deformation of the iron powder at the time of press molding, and has remarkably excellent adherence to the iron powder.
  • the Mg-Fe-O ternary-based oxide deposition film according to the present invention comprising ultra-fine grained metallic Fe particles dispersed oin the matrix contains crystalline MgO-dissolving wustite.
  • the Mg-Fe-O ternary-based oxide deposition film formed on the surface of the iron powder of the present invention and comprising ultra-fine grained metallic Fe particles dispersed in the matrix has a film-thickness in a range from 5 to 500 nm so as to ensure high magnetic flux density and high resistivity of the composite soft magnetic material formed by compacting the powder.
  • the film thickness is smaller than 5nm, it is not preferable, since the resistivity is not sufficient and eddy current loss is increased in the composite soft magnetic material formed by compacting the powder.
  • the film thickness is larger than 500 nm, it is not preferable since the magnetic flux density is decreased in the composite soft magnetic material formed by compacting the powder. More preferably, the film thickness is in a range from 5 to 200 nm.
  • the Mg-Fe-O ternary-based oxide film formed on the surface of the previously invented Mg-containing iron oxide film-coated iron powder as described in the above (f) to (k) has a sulfur-enriched layer at the boundary portion between the iron powder and the Mg-Fe-O ternary-based oxide film comprising fine metallic Fe particles dispersed in the matrix, where the sulfur concentration of the sulfur-enriched layer is higher than that of sulfur contained in a central portion of the iron powder.
  • the presence of the sulfur-enriched layer may be confirmed by performing analysis of the sulfur concentration by Auger electron spectroscopy, showing the results of the analysis, where a peak of the sulfur concentration is shown in the graph.
  • the Mg-Fe-O ternary-based oxide film comprising ultra-fine grained metallic Fe particles dispersed in the matrix has further improved bonding to the surface of iron powder, breakdown of the deposition film is prevented by tracking of the deposition film to deformation of the powder at the time of compacting the powder. High resistance is maintained by preventing contact and bonding of iron powder particles with each other at the time of heat treatment, high resistance is maintained, and therefore eddy current loss is reduced.
  • the iron powder contains sulfur as unavoidable impurities. It is considered that most of the sulfur in the sulfur-enriched layer is provided by the sulfur contained in the surface portion of the iron powder.
  • the grain size of crystals constituting the Mg-Fe-O ternary-based oxide deposition film formed on the surface of the Mg-containing iron oxide film-coated iron powder of the above (f) to (k) is as small as possible.
  • the deposition film has a fine crystalline texture having a grain size of 200 nm or less. Because the film has such a fine crystalline texture, the fine crystalline Mg-Fe-O ternary-based oxide deposition film tracks the deformation of powder particle at the time of compacting the powder, and is prevented from breakdown. At the time of heat-treating, particles of the iron powder is prevented from being made to contact and bonded with each other.
  • the powder When the powder is subjected to strain-relief heat treatment at high temperature, because of the stable property of the oxide, reduction of insulation is prevented, high resistance is maintained, and eddy current loss is lowered.
  • the grain size is larger than 200 nm, it is not preferable, because the film thickness of the Mg-Fe-O ternary-based oxide deposition film exceeds 500 nm, and magnetic flux density of compacted composite soft magnetic material is reduced.
  • the MgO content in the outermost surface of the Mg-Fe-O ternary-based oxide deposition film formd on the surface of the Mg-containing iron oxide film-coated iron powder of the above (k) is preferabley as high as possible. It is most preferable that the outermost surface is substantially composed of MgO. Where the outermost surface is substantially MgO, diffusion of Fe is inhibited at the time of heat treatment of the press-molded compact, the iron powder particles are prevented from contacting and bonding with each other, reduction of insulation is prevented, high resistance is ensured, and eddy current loss is lowered.
  • An object of the present invention is to provide a composite soft magnetic powder produced by further coating MgO-SiO 2 composite oxide film having a MgO/SiO 2 value in a range from 1.0 to 3.0 in molar ratio on the surface of the previously invented Mg-containing iron oxide film-coated iron powder as described in (f) to (k). That is, the present invention has the following aspects.
  • a composite soft magnetic powder as defined above comprising: Mg-containing iron oxide film-coated iron powder particles having iron powder particles, and Mg-Fe-O ternary-based oxide deposition films which disperse fine Fe grains in the matrices and are coated on surfaces of the iron powder particles; and MgO-SiO 2 composite oxide films which have a MgO/SiO 2 value in a range from 1.0 to 3.0 in molar ratio and are further coated on surfaces of the Mg-containing iron oxide film-coated iron powder particles.
  • a composite soft magnetic powder comprising: Mg-containing oxide film-coated iron powder particles having iron powder particles and Mg-Fe-O ternary-based oxide deposition films coated on surfaces of the iron powder particles; and MgO-SiO 2 composite oxide films which have a MgO/SiO 2 value in a range from 1.0 to 3.0 in molar ratio and are coated on surfaces of the Mg-containing oxide film-coated iron powder particles, wherein the Mg-Fe-O ternary-based oxide deposition films include fine metallic Fe grains dispersed in the matrices and have a concentration gradient where Mg and O decrease from exterior surfaces towards the interior direction, and Fe increases towards the interior direction.
  • the composite soft magnetic powder of the present invention as described in the above (54), (55), (56), (58) and (59) may be produced by: preparing a mixed oxide sol-solution of MgO and SiO 2 obtained by mixing, in volumetric ratio, alkoxysilane solution: 1 and magnesium-alkoxide solution:1 to 3; adhering the sol-solution to the surface of the Mg-containing iron oxide film-coated iron powder as described in the above (f), (g), (h), (j), or (k); and heating and drying the powder.
  • pure iron powder having a mean grain size of 70 ⁇ m and including a trace amount of sulfur as an unavoidable impurity was prepared.
  • Mg powder having a mean grain size of 50 ⁇ m was prepared.
  • Oxidation-treated iron powder having an iron oxide film on the surface was produced by performing oxidization treatment of the pure iron powder by heating the iron powder at a temperature of 220°C for 2 hours in air.
  • the obtained mixed powder was retained at a temperature of 650°C under a pressure of 2.7 ⁇ 10 -4 MPa for 1 hour, and further retained at a temperature of 200°C for 1 hour in air.
  • Mg-containing oxide film-coated iron powder 1 of the present invention having a coating of deposition film on the surface of iron powder was produced.
  • the texture of the deposition film formed on the Mg-containing oxide film-coated iron powder 1 of the present invention was observed using a transmission electron microscope and a thickness and maximum grain size of the deposition film were determined. The results are shown in Table 1.
  • electron beam diffraction patterns obtained from the Mg-containing oxide film-coated iron powder 1 of the present invention showed the presence of a MgO-dissolving wustite phase in the film.
  • the deposition film was a Mg-Fe-O ternary-based oxide deposition film at least containing (Mg, Fe)O.
  • boundary portion between the iron powder and the Mg-Fe-O ternary-based oxide deposition film was examined by a method using an Auger electron spectrometer, and the results are shown in the graph of FIG. 1 .
  • the vertical axis denotes a peak intensity of Auger electron
  • the horizontal axis denotes time of etching the coating deposition film.
  • a long etching time denotes a deep position in the coating deposition film.
  • the graph of sulfur concentration detected by Auger electron spectroscopy shows a peak of the sulfur concentration.
  • a sulfur peak of Auger electron spectrum obviously higher than the background constituted of impurity sulfur contained in the central portion of iron powder was obviously detected in the boundary portion between the deposition film and iron powder, where the boundary portion corresponded to etching time of 10 to 15 minutes.
  • the presence of a sulfur-enriched layer containing a higher concentration of sulfur than that of the core portion of iron powder was confirmed in the boundary portion between the deposition film and iron powder.
  • the Mg-containing oxide-film coated iron powder 2 comprising iron powder having a surface coating of a deposition film was produced.
  • the texture of the deposition film formed on the Mg-containing oxide film-coated iron powder 2 of the present invention was observed using a transmission electron microscope and a thickness and maximum grain size of the deposition film were determined. The results are shown in Table 1.
  • Table 1 From electron beam diffraction patterns obtained from the deposition film, it was confirmed that the film contained crystalline MgO-dissolving wustite.
  • the deposition film was a Mg-Fe-O ternary-based oxide deposition film at least containing (Mg, Fe)O, and the outermost surface of the Mg-Fe-O ternary-based oxide deposition film was composed of MgO.
  • concentration distributions of Mg, Fe, and O were examined using an Auger electron spectroscopic analyzer. As a result, the presence of a sulfur-enriched layer containing a higher concentration of sulfur than that of the core portion of iron powder was confirmed in the boundary portion between the deposition film and iron powder.
  • the Mg-containing oxide-film coated iron powder 3 of the present invention comprising iron powder having a surface coating of a deposition film was produced.
  • the texture of the deposition film was observed using a transmission electron microscope and a thickness and maximum grain size of the deposition film were determined. The results are shown in Table 1.
  • the deposition film was a Mg-Fe-O ternary-based oxide deposition film at least containing (Mg, Fe)O, and the outermost surface of the Mg-Fe-O ternary-based oxide deposition film was composed of MgO.
  • concentration distributions of Mg, Fe, and O were examined using an Auger electron spectroscopic analyzer. As a result, the presence of a sulfur-enriched layer containing a higher concentration of sulfur than that of the core portion of iron powder was confirmed in the boundary portion between the Mg-Fe-O ternary-based oxide deposition film and iron powder.
  • the Mg-containing oxide film-coated iron powders 1-3 of the present invention obtained in Examples 1 to 3 were charged in moulds, and were press-molded into compacts, thereby plate-shaped compacts each having a dimension of length: 55 mm, width: 1.0 mm, and thickness: 5 mm, and ring-shaped compacts each having a dimension of external diameter: 35 mm, internal diameter: 25 mm, and height: 5 mm were formed.
  • the obtained compacts were heat-treated under conditions of a nitrogen atmosphere, temperature: 500°C, and retention time: 30 minutes.
  • composite soft magnetic materials constituted of a plate-shaped or ring-shaped heat-treated article were produced.
  • the composite soft magnetic materials constituted of the plate shaped heat-treated articles were subjected to measurements of resistivity, and the results are shown in Table. 1. Windings were formed on the composite soft magnetic materials constituted of the ring-shaped heat-treated article, and magnetic flux density, coercive force, core loss under conditions of magnetic flux density of 1.5T and frequency of 50Hz, and core loss under conditions of magnetic flux density of 1.0T and frequency of 400Hz were measured. The results are shown in Table 1.
  • the composite soft magnetic material utilizing the Mg-containing oxide film-coated iron powder 2 of the present invention obtained in Example 2 was observed using a transmission electron microscope. As a result, an iron particle phase and grain boundary phase surrounding the iron particle phase were observed. From the electron beam diffraction pattern obtained from the grain boundary phase, it was confirmed that the grain boundary phase contained Mg-Fe-O ternary-based oxides including crystalline MgO-dissolving wustite.
  • Conventional oxide-coated iron powder 1 was produced by chemically forming Mg-containing ferrite layer on the surface of the pure iron powder prepared in Example 1.
  • the conventional oxide-coated iron powder was charged in moulds, and was press-molded into compacts, thereby a plate-shaped compact having a dimension of length: 55 mm, width: 10 mm, and thickness: 5 mm, and a ring-shaped compact having a dimension of external diameter: 35 mm, internal diameter: 25 mm, and hight: 5 mm were formed.
  • the obtained compacts were heat-treated under conditions of a nitrogen atmosphere, temperature: 500°C, and retention time: 30 minutes.
  • composite soft magnetic materials constituted of a plate-shaped or ring-shaped heat-treated article were produced.
  • the plate-shaped composite soft magnetic material was subjected to measurement of resistivity, and the result is shown in Table. 1. Winding was formed on the composite soft magnetic material constituted of the ring-shaped heat-treated article, and magnetic flux density, coercive force, core loss under conditions of magnetic flux density of 1.5T and frequency of 50Hz, and core loss under conditions of magnetic flux density of 1.0T and frequency of 400Hz were measured. The results are shown in Table 1.
  • pure iron powder having a mean grain size of 70 ⁇ m and including a trace amount of sulfur as an unavoidable impurity was prepared.
  • Mg powder having a mean grain size of 50 ⁇ m was prepared.
  • Oxidation-treated iron powder having an iron oxide film on the surface was produced by performing oxidization treatment of the pure iron powder by heating the iron powder at a temperature of 220°C for 2 hours in air.
  • the obtained mixed powder was retained at a temperature of 650°C under a pressure of 1 ⁇ 10 -4 MPa for 1 hour while being rolled.
  • Mg-containing oxide film-coated iron powder 4 of the present invention having a coating of deposition film on the surface of iron powder was produced.
  • the texture of the deposition film formed on the Mg-containing oxide film-coated iron powder 4 of the present invention was observed using a transmission electron microscope and a thickness and maximum grain size of the deposition film were determined. The results are shown in Table 2.
  • FIG. 4 is a photograph of texture taken in the observation of the sectional texture of the above-described deposition film using the transmission electron microscope. From FIG.
  • a deposition film of the present invention is coated on the surface of the iron powder (upper right), and that the deposition film has a thickness of 40nm and maximum grain size of 20nm.
  • electron beam diffraction patterns obtained from the deposition film of the present invention showed the presence of a MgO-dissolving wustite phase in the film.
  • the vertical axis denotes a peak intensity of Auger electron
  • the horizontal axis denotes time of etching the coating deposition film.
  • a long etching time denotes a deep position in the coating deposition film.
  • the deposition film of the Mg-containing oxide film-coated iron powder 4 of the present invention is a Mg-Fe-O ternary-based oxide deposition film dispersing fine Fe particles in the matrix;
  • the Mg-Fe-O ternary-based oxide deposition film has concentration gradients such that Mg and O decreases from the surface towards the interior direction, and Fe increases towards the interior direction;
  • the deposition film includes crystalline MgO-dissolving wustite phase; and the outermost surface of the deposition film was composed of MgO.
  • boundary portion between the iron powder and the Mg-Fe-O ternary-based oxide deposition film was examined by using an Auger electron spectroscopic analyzer. The results are shown in the graph of FIG. 3 .
  • the vertical axis denotes a peak intensity of Auger electron
  • the horizontal axis denotes time of etching the coating deposition film. As long an etching time denotes as deep a position in the coating deposition film.
  • the graph of sulfur concentration detected by Auger electron spectroscopy shows a peak of the sulfur concentration.
  • the deposition film is a Mg-Fe-O ternary-based oxide deposition film dispersing fine Fe particles in the matrix; the deposition film includes crystalline MgO-dissolving wustite phase; and the outermost surface of the deposition film was composed of MgO.
  • the texture of the deposition film was observed using a transmission electron microscope and a thickness and maximum grain size of the deposition film were determined. The results are shown in Table 2. In addition, from the electron beam diffraction pattern obtained from the deposition film, it was confirmed that the film included crystalline MgO-dissolving wustite phase.
  • the deposition film formed on the surface of Mg-containing oxide film-coated iron powder 6 of the present invention using an X-ray photoelectron spectrometer, from the bonding energies, it was confirmed that at least fine metallic Fe particles were dispersed in the matrix of the deposition film, the deposition film included MgO dissolving wustite phase, and that the outermost surface of the Mg-Fe-O ternary-based oxide deposition film was composed of MgO.
  • the deposition film of the Mg-containing oxide film-coated iron powder 6 of the present invention is a Mg-Fe-O ternary-based oxide deposition film, the deposition film includes crystalline MgO-dissolving wustite phase, and the outermost surface of the deposition film is composed of MgO.
  • concentration distributions of Mg,O, and Fe of the deposition film was examined using an Auger electron spectroscopic analyzer. As a result, it was confirmed that: the deposition film had concentration gradients such that Mg and O decreased from the surface towards the interior direction, and Fe increased towards the interior direction; and that a sulfur-enriched layer containing a higher concentration of sulfur than that of the core portion of iron powder was present in the boundary portion between the iron pwder and the Mg-Fe-O ternary-based oxide deposition film.
  • the Mg-containing oxide film-coated iron powders 4-6 of the present invention obtained in Examples 4 to 6 were charged in moulds, and were press-molded into compacts, thereby plate-shaped compacts each having a dimension of length: 55 mm, width: 10 mm, and thickness: 5 mm, and ring-shaped compacts each having a dimension of external diameter: 35 mm, internal diameter: 25 mm, and height: 5 mm were formed.
  • the obtained compacts were heat-treated under conditions of a nitrogen atmosphere, temperature: 500°C, and retention time: 30 minutes.
  • composite soft magnetic materials constituted of a plate-shaped or ring-shaped heat-treated article were produced.
  • the plate-shaped composite soft magnetic materials were subjected to measurements of resistivity, and the results are shown in Table.2.
  • Windings were formed on the composite soft magnetic materials constituted of the ring-shaped heat-treated article, and magnetic flux density, coercive force, core loss under conditions of magnetic flux density of 1.5T and frequency of 50Hz, and core loss under conditions of magnetic flux density of 1.0T and frequency of 400Hz were measured.
  • the results are shown in Table 2.
  • composite soft magnetic materials utilizing the Mg-containing oxide film coated iron powder 4 to 6 of the present invention obtained in Example 4 to 6 were observed using a transmission electron microscope.
  • iron particle phase originated from the iron powder and grain boundary phase surrounding the iron particle phase were observed in each of the composite soft magnetic materials. From the electron beam diffraction patterns obtained from the grain boundary phases, it was confirmed that the grain boundary phases contained Mg-Fe-O ternary-based oxides including crystalline MgO-dissolving wustite phase.
  • Conventional oxide-coated iron powder 2 was produced by chemically forming Mg-containing ferrite layer on the surface of the pure iron powder prepared in Example 4.
  • the conventional oxide-coated iron powder 2 was charged in moulds, and was press-molded into compacts, thereby a plate-shaped compact having a dimension of length: 55 mm, width: 10 mm, and thickness: 5 mm, and a ring-shaped compact having a dimension of external diameter: 35 mm, internal diameter: 25 mm, and height: 5 mm were formed.
  • the obtained compacts were heat-treated under conditions of a nitrogen atmosphere, temperature: 500°C, and retention time: 30 minutes.
  • composite soft magnetic materials constituted of a plate-shaped or ring-shaped heat-treated article were produced.
  • the composite soft magnetic material constituted of the plate-shaped heat-treated article was subjected to measurement of resistivity, and the result is shown in Table.2. Winding was formed on the composite soft magnetic material constituted of the ring-shaped heat-treated article, and magnetic flux density, coercive force, core loss under conditions of magnetic flux density of 1.5T and frequency of 50Hz, and core loss under conditions of magnetic flux density of 1.0T and frequency of 400Hz were measured. The results are shown in Table 2.
  • the present invention has an excellent effect in terms of electric and electronic industries.
  • a composite soft magnetic materials is produced by press molding Mg-containing oxide film-coated iron powder of the present invention having Mg-Fe-O ternary-based oxide deposition film dispersing extremely fine metallic Fe particles in the matrix
  • the Mg-Fe-O ternary-based oxide deposition film has high toughness by the presence of extremely fine metallic Fe particles dispersed in the matrix, and is scarcely broken down during the press molding of the Mg-containing oxide film-coated iron powder. Therefore, the obtained composite soft magnetic material has high resistivity, and low eddy current loss, low coercive force, and low hysteresis loss.
  • the present invention it is possible to produce composite soft magnetic materials having such properties. Therefore, the present invention has effective contribution to electric and electronic industries.
  • the present invention it is possible to provide composite soft magnetic materials having high strength, high resistance, and high magnetic flux density. Therefore, the present invention has effective contribution to electric and electronic industries.

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Abstract

L'invention concerne une poudre de fer enrobée d'oxyde utilisée dans la production de diverses parties de circuits électromagnétiques nécessitant une résistance spécifique élevée. L'invention se rapporte à une poudre de fer (Fe) enrobée d'oxyde contenant du magnésium (Mg) comprenant une poudre de fer dont la surface est enrobée d'un film de dépôt d'oxyde ternaire Mg-Fe-O contenant au moins (Mg,Fe)O, où (Mg,Fe)O est une wustite cristalline renfermant MgO solide dissout et où le film de dépôt d'oxyde ternaire possède dans une zone d'interface contenant de la poudre de fer, une couche enrichie en souffre ayant une concentration en soufre plus élevée que dans la zone centrale de la poudre de fer, et possède également une structure microcristalline dont le diamètre granulométrique cristallin est < 200nm et dont la surface la plus externe est constituée principalement de MgO. L'invention concerne également une substance magnétique douce composite utilisée dans la poudre de fer (Fe) enrobée d'oxyde contenant Mg.

Claims (14)

  1. Poudre de fer enrobée d'un film d'oxyde contenant du magnésium comprenant des particules de poudre de fer et des films de dépôt d'oxyde à base ternaire Mg-Fe-O qui contiennent au moins (Mg, Fe)O et sont appliqués sur des surfaces des particules de poudre de fer,
    dans laquelle le (Mg, Fe)O contenu dans les films de dépôt d'oxyde à base ternaire Mg-Fe-O est une phase wustite de dissolution de MgO cristalline.
  2. Poudre de fer enrobée d'un film d'oxyde contenant du magnésium selon la revendication 1, comprenant en outre des couches enrichies en soufre dans des parties limitrophes entre les particules de poudre de fer et les films de dépôt d'oxyde à base ternaire Mg-Fe-O contenant au moins (Mg, Fe)O, dans laquelle les concentrations de soufre des couches enrichies en soufre sont supérieures à celles du soufre contenu en tant qu'impureté inévitable dans des parties centrales des particules de poudre de fer.
  3. Poudre de fer enrobée d'un film d'oxyde contenant du magnésium selon la revendication 1 ou 2, dans laquelle les films de dépôt d'oxyde à base ternaire Mg-Fe-O contenant au moins (Mg, Fe)O ont des structures microcristallines ayant une grosseur de grain inférieure ou égale à 200 nm.
  4. Poudre de fer enrobée d'un film d'oxyde contenant du magnésium selon la revendication 1, 2 ou 3, dans laquelle les surfaces le plus à l'extérieur des films de dépôt d'oxyde à base ternaire Mg-Fe-O contenant au moins (Mg, Fe)O sont sensiblement composées de MgO.
  5. Poudre de fer enrobée d'un film d'oxyde contenant du magnésium selon la revendication 1, dans laquelle les films de dépôt d'oxyde à base ternaire Mg-Fe-O comprennent des grains de Fe métalliques ultrafins dispersés dans les films.
  6. Poudre de fer enrobée d'un film d'oxyde contenant du magnésium selon la revendication 5, dans laquelle les films de dépôt d'oxyde à base ternaire Mg-Fe-O comprenant des grains de Fe métalliques ultrafins dispersées dans les films ont des gradients de concentration où Mg et O diminuent à partir des surfaces extérieures vers la direction intérieure, et Fe augmente vers la direction intérieure.
  7. Poudre de fer enrobée d'un film d'oxyde contenant du magnésium selon la revendication 5 ou 6, comprenant en outre des couches enrichies en soufre dans des parties limitrophes entre les particules de poudre de fer et les films de dépôt d'oxyde à base ternaire Mg-Fe-O comprenant des grains de Fe métalliques ultrafins dispersés dans les films, dans laquelle les concentrations de soufre des couches enrichies en soufre sont supérieures à celles du soufre contenu en tant qu'impuretés inévitables dans des parties centrales des particules de poudre de fer.
  8. Poudre de fer enrobée d'un film d'oxyde contenant du magnésium selon la revendication 5, 6 ou 7, dans laquelle les films de dépôt d'oxyde à base ternaire Mg-Fe-O comprenant des grains de Fe métalliques ultrafins dispersés dans les films ont des structures microcristallines ayant une taille de grain inférieure ou égale à 200 nm.
  9. Poudre de fer enrobée d'un film d'oxyde contenant du magnésium selon la revendication 5, 6, 7 ou 8, dans laquelle les surfaces le plus à l'extérieur des films de dépôt d'oxyde à base ternaire Mg-Fe-O comprenant des grains de Fe métalliques ultrafins dispersés dans les films sont sensiblement composées de MgO.
  10. Poudre de fer enrobée d'un film d'oxyde contenant du magnésium selon la revendication 1, 2, 3, 4, 5, 6, 7, 8 ou 9, comprenant en outre des films d'oxyde composites de MgO-SiO2 qui ont une valeur de MgO/SiO2 dans une plage de 1,0 à 3,0 en rapport molaire et sont en outre appliqués sur des surfaces des particules de poudre de fer enrobées d'un film d'oxyde de fer contenant du magnésium.
  11. Matériau magnétique tendre composite qui a été produit au moyen d'une poudre selon l'une quelconque des revendications 1 à 10, comprenant une phase de particules de fer et une phase de joint de grain entourant la phase de particules de fer, dans laquelle la phase de joint de grain contient de l'oxyde à base ternaire Mg-Fe-O qui comprend une phase wustite de dissolution de MgO cristalline.
  12. Composant de circuit électromagnétique comprenant un matériau magnétique tendre selon la revendication 11.
  13. Composant de circuit électromagnétique selon la revendication 12, dans lequel le composant de circuit magnétique est un noyau d'aimant, un noyau de moteur, un noyau de générateur, un noyau de solénoïde, un noyau d'allumage, un réacteur, un transformateur, un noyau de bobine d'arrêt ou un noyau de capteur magnétique.
  14. Dispositif électrique équipé d'un composant de circuit électromagnétique selon la revendication 12 ou 13.
EP05805498A 2005-01-25 2005-11-02 Poudre de fer enrobee d'oxyde contenant du magnesium Active EP1852199B1 (fr)

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JP2005155206A JP4761835B2 (ja) 2005-01-25 2005-05-27 Ｍｇ含有酸化膜被覆鉄粉末
JP2005155207A JP4761836B2 (ja) 2005-01-25 2005-05-27 Ｍｇ含有酸化膜被覆鉄粉末
JP2005158893A JP5027390B2 (ja) 2005-03-28 2005-05-31 堆積膜被覆鉄粉末
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JP2005158892A JP2006324612A (ja) 2005-04-20 2005-05-31 堆積酸化膜被覆鉄シリコン粉末およびその粉末の圧粉焼成体からなる複合軟磁性材
JP2005161480A JP4480628B2 (ja) 2005-06-01 2005-06-01 複合軟磁性粉末およびその製造方法
JP2005161479A JP4480627B2 (ja) 2005-06-01 2005-06-01 複合軟磁性粉末およびその製造方法
JP2005231191 2005-08-09
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EP2502689A2 (fr) 2012-09-26
WO2006080121A1 (fr) 2006-08-03
CA2598842A1 (fr) 2006-08-03
US20090174512A1 (en) 2009-07-09
EP1852199A1 (fr) 2007-11-07
EP2248617B1 (fr) 2017-06-21
EP2502689B1 (fr) 2014-04-30
EP2248617A2 (fr) 2010-11-10
US20120138844A1 (en) 2012-06-07
EP2502689B8 (fr) 2014-06-11
EP2502689A3 (fr) 2013-07-24
US9269481B2 (en) 2016-02-23
EP2248617A3 (fr) 2013-05-01
US8481178B2 (en) 2013-07-09
EP1852199A4 (fr) 2010-03-17

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